JPH0557838A - Surface treated steel plate excellent in resistance to blackening of worked part and adhesion of coating - Google Patents
Surface treated steel plate excellent in resistance to blackening of worked part and adhesion of coatingInfo
- Publication number
- JPH0557838A JPH0557838A JP24481391A JP24481391A JPH0557838A JP H0557838 A JPH0557838 A JP H0557838A JP 24481391 A JP24481391 A JP 24481391A JP 24481391 A JP24481391 A JP 24481391A JP H0557838 A JPH0557838 A JP H0557838A
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- Prior art keywords
- coating
- film
- adhesion
- treated steel
- steel plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【００１】[001]
【産業上の利用分野】本発明は、加工部耐黒変性および
塗膜密着性に優れた表面処理鋼板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated steel sheet which is excellent in blackening resistance of a worked portion and has excellent coating film adhesion.
【００２】[002]
【従来技術】近年、自動車、家電、建築分野などで使用
するめっき鋼板は、耐食性のほかに塗装前処理省略化に
よる直接塗装性、加工性、耐指紋性などが要求されてい
る。このため、後処理としては単にクロメート処理を施
しただけでは不十分なことから、クロメート皮膜の上に
膜厚５μｍ以下の薄い有機樹脂皮膜を形成して対応して
いる。また、一部には有機樹脂皮膜中に潤滑剤を添加し
て、さらに加工性を向上させたものもある。2. Description of the Related Art In recent years, plated steel sheets used in the fields of automobiles, home appliances, construction, etc. are required to have not only corrosion resistance but also direct paintability, workability and fingerprint resistance by omitting pretreatment for painting. For this reason, since it is not sufficient to simply perform the chromate treatment as the post-treatment, a thin organic resin film having a film thickness of 5 μm or less is formed on the chromate film. In addition, there is a part in which a lubricant is added to the organic resin film to further improve the workability.
【００３】この表面処理鋼板は、連続めっきラインのク
ロメート処理槽の後方にコ−タ−と乾燥炉を設けて、有
機樹脂皮膜を形成すれば、容易かつ安価に製造できる。
しかし、クロメート処理槽通過後の鋼板は常温まで低下
していないので、有機樹脂液が有機溶媒を含んでいる
と、板温による発火や爆発の危険がある。このため、有
機樹脂皮膜の形成は、水可溶性もしくは水分散性のエマ
ルジョンを塗布する方法により行われている場合が多
い。This surface-treated steel sheet can be easily and inexpensively manufactured by providing a coater and a drying oven behind the chromate treatment tank of the continuous plating line to form an organic resin film.
However, since the steel sheet after passing through the chromate treatment tank has not been cooled to room temperature, if the organic resin liquid contains an organic solvent, there is a risk of ignition or explosion due to the plate temperature. Therefore, the organic resin film is often formed by a method of applying a water-soluble or water-dispersible emulsion.
【００４】エマルジョン化できる有機樹脂としては、種
々あるが、従来より使用されているのは、塗膜密着性、
耐食性に優れた（メタ）アクリル樹脂で、ポリ（メタ）
アクリル酸およびその共重合体、ポリ（メタ）アクリル
酸エステルおよびその共重合体などであり、共重合させ
るモノマ−としては、アクリロニトリル、アクリルアミ
ド、ブタジエン、ビニルアセテ−トなどが用いられてい
た。There are various organic resins that can be emulsified, but the ones that have been used conventionally are coating film adhesion,
Poly (meth) acrylic resin with excellent corrosion resistance
Acrylic acid and its copolymers, poly (meth) acrylic acid ester and its copolymers, etc., and acrylonitrile, acrylamide, butadiene, vinyl acetate, etc. were used as the monomers to be copolymerized.
【００５】[0095]
【発明が解決しようとする課題】しかしながら、このよ
うなアクリル樹脂皮膜は、皮膜に潤滑剤を添加しても、
鋼板にプレス加工や曲げ加工を施すと、金型と皮膜間の
摺動摩擦により加工部が黒変してしまう。この黒変の発
生原因は明らかではないが、皮膜表面の潤滑特性、皮膜
硬度、樹脂の熱分解温度が関係しているようである。潤
滑剤の添加量を多くすれば、若干改善されるが、完全に
解消できず、潤滑剤の増量は逆に上塗り塗膜との密着性
低下を招いてしまう。本発明は、これらの欠点を解消し
た有機樹脂被覆の表面処理鋼板を提供するものである。However, in such an acrylic resin film, even if a lubricant is added to the film,
When a steel plate is pressed or bent, sliding friction between the die and the coating causes the processed part to turn black. The cause of this black discoloration is not clear, but it seems that the lubrication characteristics of the film surface, the film hardness, and the thermal decomposition temperature of the resin are related. Although a slight improvement can be achieved by increasing the amount of the lubricant added, the amount cannot be completely eliminated, and the increase in the amount of the lubricant, on the contrary, leads to a decrease in adhesion to the top coat film. The present invention provides a surface-treated steel sheet coated with an organic resin, which solves these drawbacks.
【００６】[0096]
【課題を解決するための手段】本発明は、有機樹脂皮膜
をスチレン成分がモル比率で１０〜４０％である（メ
タ）アクリル−スチレン共重合体皮膜にし、潤滑性を高
めたい場合には潤滑剤を樹脂１００重量部当り１〜２５
重量部添加した。According to the present invention, an organic resin film is a (meth) acrylic-styrene copolymer film having a styrene component in a molar ratio of 10 to 40%, and lubrication is desired when lubricity is desired to be improved. 1 to 25 per 100 parts by weight of resin
Parts by weight was added.
【００７】[0097]
【作用】アクリル樹脂は、モノマ−の種類や組成により
皮膜特性が変化するが、一般に柔らかく、上塗り塗膜と
の密着性が優れている。一方、ポリスチレン樹脂は、硬
く、強靭であり、また、フェニル基を有しているため、
耐熱性に優れている。しかし、上塗り塗膜との密着性は
劣る。The function of the acrylic resin varies depending on the type and composition of the monomer, but it is generally soft and has excellent adhesion to the top coating film. On the other hand, polystyrene resin is hard and tough, and because it has a phenyl group,
Excellent heat resistance. However, the adhesion with the top coating film is poor.
【００８】そこで、鋼板の有機樹脂皮膜をアクリルモノ
マ−とスチレンモノマ−の共重合体にすれば、加工部の
耐黒変性と上塗り塗装性とを備えたものにすることがで
きる。しかし、図１、図２に示すように、スチレン成分
がモル比率で１０％未満であると、耐黒変性が低下し、
４０％を越えると、上塗り塗膜との密着性が低下してし
まう。Therefore, if the organic resin film of the steel sheet is made of a copolymer of acrylic monomer and styrene monomer, it is possible to provide the processed portion with blackening resistance and top coatability. However, as shown in FIGS. 1 and 2, if the styrene component is less than 10% in terms of molar ratio, the blackening resistance is lowered,
If it exceeds 40%, the adhesion to the top coating film will decrease.
【００９】すなわち、図１は、クロメート処理した電気
亜鉛めっき鋼板（板厚０.６ｍｍ、めっき付着量２０ｇ
／ｍ2）にスチレンモル比率の異なるブチルアクリレ−
トとエチルアクリレ−トとの共重合体を塗布して、乾燥
した後、アクリル系溶剤型塗料［日本ペイント（株）製
ス−パ−ラックＦ４７］を塗装、乾燥して調製した表面
処理鋼板にドロ−ビ−ド加工（加圧力２０００Ｎ、引き
抜き速度５００ｍｍ／ｍｉｎ）を施して、加工部の黒変
化程度を評価したものであるが、スチレン成分のモル比
率が１０％未満になると、耐黒変性は急激に低下する。That is, FIG. 1 shows a chromate-treated electrogalvanized steel sheet (sheet thickness: 0.6 mm, coating weight: 20 g).
/ M 2 ) butyryl acrylate with different styrene molar ratio
To a surface-treated steel sheet prepared by coating and drying an acrylic solvent-based paint [Super Paint F47 manufactured by Nippon Paint Co., Ltd.] after coating a copolymer of ethyl acetate and ethyl acrylate. The degree of black change of the processed part was evaluated by subjecting it to draw bead processing (pressure of 2000 N, drawing speed of 500 mm / min). When the molar ratio of the styrene component was less than 10%, it was resistant to blackening. Drops sharply.
【０１０】また、図２は、前記同様に調製した表面処理
鋼板を沸水中に２時間浸漬して、上塗り塗膜の密着性を
調査したものであるが、共重合体のスチレンモル比率が
４０％を越えると、耐水密着性が急激に低下するのがわ
かる。なお、塗膜密着性調査は、ゴバン目４ｍｍ張り出
し加工した部分にセロテ−プを貼付けた後、剥離して、
塗膜残存率（％）を算出する方法で行った。Further, FIG. 2 shows the surface-treated steel sheet prepared in the same manner as described above, which was immersed in boiling water for 2 hours to examine the adhesion of the top coating film. The styrene molar ratio of the copolymer was 40%. It can be seen that the water-proof adhesiveness sharply deteriorates when it exceeds. In addition, the adhesion of the coating film was examined by applying a sero tape to the portion where the burring pattern 4 mm was overhang, and then peeling it off.
It was performed by a method of calculating the coating film residual rate (%).
【０１１】皮膜の（メタ）アクリル−スチレン共重合体
のアクリル成分は、メチル（メタ）アクリレ−ト、エチ
ル（メタ）アクリレ−ト、ブチル（メタ）アクリレ−ト
などの（メタ）アクリル酸エステルが好ましい。皮膜厚
は、５μｍ以下、好ましくは０.１〜２.０μｍが適して
いる。The acrylic component of the (meth) acrylic-styrene copolymer of the film is a (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate. Is preferred. A suitable film thickness is 5 μm or less, preferably 0.1 to 2.0 μm.
【０１２】本発明でのめっき鋼板としては、亜鉛、亜鉛
−鉄合金、亜鉛−ニッケル合金、亜鉛−マンガン合金、
亜鉛−アルミニウム合金、亜鉛−マグネシウム合金また
は亜鉛−コバルト−クロム合金などの亜鉛系めっき鋼
板、アルミニウム、アルミニウム−シリコン合金、アル
ミニウム−クロム合金、アルミニウム−マンガン合金、
アルミニウム−ニッケル合金などのアルミニウム系めっ
き鋼板および銅、銅合金などの銅系めっき鋼板などが掲
げられる。As the plated steel sheet in the present invention, zinc, zinc-iron alloy, zinc-nickel alloy, zinc-manganese alloy,
Zinc-aluminum alloy, zinc-plated steel sheet such as zinc-magnesium alloy or zinc-cobalt-chromium alloy, aluminum, aluminum-silicon alloy, aluminum-chromium alloy, aluminum-manganese alloy,
Examples thereof include aluminum-based plated steel sheets such as aluminum-nickel alloys and copper-based plated steel sheets such as copper and copper alloys.
【０１３】また、クロメート皮膜は、従来のクロメート
処理法で形成したものでよい。クロメート処理には、塗
布型、反応型、電解型などがあるが、これらのいずれの
処理法で形成したものでもよい。クロメート皮膜量は、
５〜２００ｍｇ／ｍ2の範囲が好ましい。The chromate film may be formed by a conventional chromate treatment method. The chromate treatment includes a coating type, a reaction type, an electrolytic type and the like, but any of these treatment methods may be used. The amount of chromate film is
The range of 5 to 200 mg / m 2 is preferable.
【０１４】有機樹脂皮膜に潤滑剤を添加する場合の潤滑
剤としては、例えば、有機系のものの場合、ポリエチレ
ンワックス、天然パラフィンなどの炭化水素系のもの、
ラウリル酸、ステアリン酸などの脂肪酸系のもの、脂肪
酸の低級アルコ−ルエステルまたは多価アルコ−ルエス
テルのようなエステル系のものを添加すればよい。ま
た、無機系のものとしては、グラファイト、二硫化モリ
ブデン、二硫化タングステンなどを添加すればよい。As a lubricant when a lubricant is added to the organic resin film, for example, in the case of an organic lubricant, a hydrocarbon wax such as polyethylene wax or natural paraffin,
Fatty acid-based ones such as lauric acid and stearic acid, and ester-based ones such as lower alcohol esters or polyhydric alcohol esters of fatty acids may be added. As an inorganic material, graphite, molybdenum disulfide, tungsten disulfide, or the like may be added.
【０１５】潤滑剤の添加量は、樹脂１００重量部当り１
重量部未満であると、添加効果が小さく、２５重量部を
越えると、上塗り塗膜との密着性が低下し、エマルジョ
ンへの分散不良やゲル化が生じ、鋼板との密着性も低下
するため、１〜２５重量部にする。The amount of the lubricant added is 1 per 100 parts by weight of the resin.
If it is less than 25 parts by weight, the effect of addition is small, and if it exceeds 25 parts by weight, the adhesion with the top coating film is reduced, dispersion in emulsion or gelation occurs, and the adhesion with the steel sheet is also reduced. , 1 to 25 parts by weight.
【０１６】[0163]
【実施例】電気Ｚｎ−１２.３％Ｎｉ合金めっき鋼板
（板厚０.７ｍｍ、めっき付着量３０ｇ／ｍ2）および溶
融Ａｌ−９.０％Ｓｉ合金めっき鋼板（板厚１.０ｍｍ、
めっき付着量４０ｇ／ｍ2）に下記条件でそれぞれ塗布
型クロメート処理および反応型クロメート処理を施し
て、第１表、第２表に示すような組成のアクリル−スチ
レン共重合体のエマルジョンまたはこれに潤滑剤を添加
したものを塗布した。[Embodiment] Electric Zn-12.3% Ni alloy-plated steel sheet (plate thickness 0.7 mm, coating amount 30 g / m 2 ) and molten Al-9.0% Si alloy-plated steel sheet (plate thickness 1.0 mm,
A coating amount of 40 g / m 2 ) was subjected to coating-type chromate treatment and reactive-type chromate treatment under the following conditions to obtain an acrylic-styrene copolymer emulsion having the composition shown in Tables 1 and 2 or this. The one to which the lubricant was added was applied.
【０１７】（１）塗布型クロメート処理 全Ｃｒ２５ｇ／ｌ、Ｃｒ3+／全Ｃｒの比０.４、シリカ
ゾル７５ｇ／ｌ、リン酸８ｇ／ｌ、ホウ酸２ｇ／ｌから
なる処理液をロ−ルコ−タ−でめっき鋼板に塗布して、
水洗することなく２００℃で乾燥し、全Ｃｒ量が５０ｍ
ｇ／ｍ2のクロメート皮膜を形成した。(1) Coating-type chromate treatment A treatment liquid containing 25 g / l of total Cr, 0.4 of Cr 3+ / total Cr, 75 g / l of silica sol, 8 g / l of phosphoric acid, and 2 g / l of boric acid was applied. Apply it to the plated steel plate with a coater,
Dry at 200 ℃ without washing with water, and the total Cr content is 50m
A chromate film of g / m 2 was formed.
【０１８】（１）反応型クロメート処理 無水クロム酸８ｇ／ｌ、リン酸１５ｇ／ｌ、フッ酸１ｇ
／ｌからなる処理液にめっき鋼板を浸漬して、引き上げ
後絞りロ−ル間を通過させて、全Ｃｒ量が２０ｍｇ／ｍ
2のクロメート皮膜を形成した。(1) Reactive Chromate Treatment 8 g / l of chromic anhydride, 15 g / l of phosphoric acid, 1 g of hydrofluoric acid
The plated steel sheet is dipped in a treatment liquid consisting of 1 / l, pulled up, and then passed between drawing rolls so that the total amount of Cr is 20 mg / m 2.
A chromate film of 2 was formed.
【０１９】また、アクリル−スチレン共重合体エマルジ
ョンへの潤滑剤添加は、樹脂１００重量部当り１０〜１
５重量部添加し、乾燥は潤滑剤の添加の有無に関係なく
いずれも１００℃で行い、乾燥塗膜厚を１.０〜１.５μ
ｍにした。The lubricant is added to the acrylic-styrene copolymer emulsion in an amount of 10 to 1 per 100 parts by weight of the resin.
5 parts by weight is added, and the drying is performed at 100 ° C. with or without addition of a lubricant, and the dry coating film thickness is 1.0 to 1.5 μm.
It was set to m.
【０２０】以上のようにして製造した表面処理鋼板に次
の試験を実施した。 （１）ドロ−ビ−ド試験 加圧力２０００Ｎ、引き抜き速度５００ｍｍ／ｍｉｎの
条件で実施し、黒変全くなし○、一部黒変△、全面黒変
×で評価した。The surface-treated steel sheet produced as described above was subjected to the following tests. (1) Drop-bead test The test was carried out under the conditions of a pressing force of 2000 N and a drawing speed of 500 mm / min.
【０２１】（２）塗膜密着性試験 アクリル系溶剤型塗料［日本ペイント（株）製ス−パ−
ラックＦ４７］を乾燥塗膜厚が３０μｍになるように塗
装して、１６０℃で１０分間乾燥した後、冷却して、ゴ
バン目４ｍｍ張り出し加工し、加工部にセロテ−プを貼
付け、剥離し、塗膜残存率（％）を算出した。第３表に
この結果を示す。(2) Coating film adhesion test Acrylic solvent-based paint [Super paint manufactured by Nippon Paint Co., Ltd.]
[Rack F47] is applied to give a dry coating film thickness of 30 μm, dried at 160 ° C. for 10 minutes, cooled, and subjected to a burring 4 mm overhang process, and a serrated tape is attached to the processed part and peeled off. The coating film residual rate (%) was calculated. The results are shown in Table 3.
【０２２】[0222]
【第１表】 ＭＡ：メチルアクリレ−ト、ＢＡ：ブチルアクリレ−
ト、ＥＡ：エチルアクリレ−ト、２ＥＨＡ：２−エチル
ヘキシルアクリレ−ト、Ａｃ：アクリル酸[Table 1] MA: methyl acrylate, BA: butyl acrylate
, EA: ethyl acrylate, 2EHA: 2-ethylhexyl acrylate, Ac: acrylic acid
【０２３】[0233]
【第２表】 [Table 2]
【０２４】[0241]
【第３表】 [Table 3]
【０２５】[025]
【発明の効果】以上のように、本発明の表面処理鋼板
は、加工を施した場合の耐黒変性および塗膜密着性が向
上する。As described above, the surface-treated steel sheet of the present invention has improved resistance to blackening and coating adhesion when processed.
【図１】アクリル−スチレン共重合体皮膜のスチレン成
分量と加工部耐黒変性との関係を示すグラフである。FIG. 1 is a graph showing the relationship between the amount of styrene component in an acrylic-styrene copolymer film and the blackening resistance of a processed part.
【図２】アクリル−スチレン共重合体皮膜のスチレン成
分量と上塗り塗膜に対する密着性との関係を示すグラフ
である。FIG. 2 is a graph showing the relationship between the amount of styrene component of the acrylic-styrene copolymer film and the adhesion to the top coat film.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内田 幸夫 大阪府堺市石津西町５番地 日新製鋼株式 会社鉄鋼研究所表面処理研究部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Uchida 5 Ishizushi Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd.
Claims (2)
成し、そのクロメート皮膜の上に有機樹脂皮膜を形成し
た表面処理鋼板において、有機樹脂皮膜をスチレン成分
がモル比率で１０〜４０％である（メタ）アクリル−ス
チレン共重合体皮膜にしたことを特徴とする加工部耐黒
変性および塗膜密着性に優れた表面処理鋼板。1. A surface-treated steel sheet having a chromate film formed on the surface of a plated steel sheet and an organic resin film formed on the chromate film, wherein the organic resin film has a styrene component in a molar ratio of 10 to 40%. ) A surface-treated steel sheet having an excellent resistance to blackening of the processed portion and adhesion of the coating film, which is characterized in that it is an acrylic-styrene copolymer film.
皮膜に潤滑剤を樹脂１００重量部当り１〜２５重量部添
加したことを特徴とする加工部耐黒変性および塗膜密着
性に優れた表面処理鋼板。2. A surface excellent in blackening resistance of a processed part and adhesion of a coating film, wherein a lubricant is added to a (meth) acrylic-styrene copolymer film in an amount of 1 to 25 parts by weight per 100 parts by weight of a resin. Treated steel plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24481391A JPH0557838A (en) | 1991-08-30 | 1991-08-30 | Surface treated steel plate excellent in resistance to blackening of worked part and adhesion of coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24481391A JPH0557838A (en) | 1991-08-30 | 1991-08-30 | Surface treated steel plate excellent in resistance to blackening of worked part and adhesion of coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0557838A true JPH0557838A (en) | 1993-03-09 |
Family
ID=17124336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24481391A Withdrawn JPH0557838A (en) | 1991-08-30 | 1991-08-30 | Surface treated steel plate excellent in resistance to blackening of worked part and adhesion of coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0557838A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6731375B2 (en) | 2000-12-14 | 2004-05-04 | Semiconductor Leading Edge Technologies, Inc. | Projection aligner, exposing method and semiconductor device |
| JP2010208278A (en) * | 2009-03-12 | 2010-09-24 | Nisshin Steel Co Ltd | Transparent coating-applied stainless steel sheet |
-
1991
- 1991-08-30 JP JP24481391A patent/JPH0557838A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6731375B2 (en) | 2000-12-14 | 2004-05-04 | Semiconductor Leading Edge Technologies, Inc. | Projection aligner, exposing method and semiconductor device |
| JP2010208278A (en) * | 2009-03-12 | 2010-09-24 | Nisshin Steel Co Ltd | Transparent coating-applied stainless steel sheet |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19981112 |